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WO2018101794A2 - Système catalyseur métallocène comprenant une composition fonctionnellement stable, et procédé de production de polyoléfine au moyen d'un système catalyseur métallocène - Google Patents

Système catalyseur métallocène comprenant une composition fonctionnellement stable, et procédé de production de polyoléfine au moyen d'un système catalyseur métallocène Download PDF

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WO2018101794A2
WO2018101794A2 PCT/KR2017/014020 KR2017014020W WO2018101794A2 WO 2018101794 A2 WO2018101794 A2 WO 2018101794A2 KR 2017014020 W KR2017014020 W KR 2017014020W WO 2018101794 A2 WO2018101794 A2 WO 2018101794A2
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carbon atoms
catalyst system
metallocene catalyst
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WO2018101794A3 (fr
WO2018101794A9 (fr
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최혜선
김동옥
서준호
정동욱
허은정
정의갑
최승일
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Hanwha Chemical Corp
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
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    • C08F4/00—Polymerisation catalysts
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a metallocene catalyst system comprising a composition for operating stability and a method for producing polyolefin using the same, and more particularly, stable process operation by maintaining the intrinsic activity of the catalyst during the olefin polymerization and minimizing fouling and aggregation phenomenon It relates to a metallocene catalyst system and a polyolefin production method and polyolefin using the same.
  • various polymerization catalysts such as Ziegler-Natta catalysts, chromium catalysts or metallocene catalysts are used depending on the type of the central metal. These polymerization catalysts are selectively used according to each production process and application because of different catalytic activity, molecular weight distribution characteristics of the polyolefins prepared using the same, and reaction characteristics with respect to comonomers.
  • metallocene is basically a transition metal or transition metal halogen compound having a coordination bond of a cyclopentadienyl ligand, and has various molecular structures according to changes in ligand form and central metal.
  • the metallocene compound alone is inactive as a polymerization catalyst, is activated as a cation by the action of a promoter such as methylaluminoxane (MAO), and at the same time, the promoter is coordinated as an anion that does not coordinate with the metallocene compound.
  • the unsaturated cationic active species are stabilized to form a catalyst system having activity in various olefin polymerizations.
  • the characteristics of the metallocene catalyst are that since the polymer has a uniform activity point, the polymer has a narrow molecular weight distribution, is easy to copolymerize, has a uniform distribution of comoners, and can adjust the steric structure of the polymer according to the symmetry of the catalyst. .
  • a solution polymerization process is polymerization in the state that the polymer is melted in the liquid phase
  • the slurry polymerization process is the polymerization in suspension state, in which the polymer produced in the liquid polymerization medium is dispersed in the solid state.
  • the gas phase polymerization process a polymer produced in a gas phase polymerization medium is dispersed in a fluidized state.
  • a slurry polymerization process is a suspension in which a polymer is polymerized and dispersed in a liquid medium, and polymer particles may agglomerate with each other depending on reaction conditions. May cause operability problems.
  • the gas phase polymerization process is performed at a temperature lower than the melting point of the polymer to be formed, which also causes the polymer particles to soften and agglomerate or stick to the reaction apparatus when the temperature rises above the critical temperature for several reasons. Therefore, in the gas phase polymerization process, fouling may occur frequently on the inner wall of the circulating gas line, the heat exchanger, the inner wall of the cooler, and agglomeration near the softening point of the polyolefin. This phenomenon may be influenced by the polymerization medium, the molecular weight, the concentration of the comonomer, and the like. In addition, this phenomenon may be intensified as the concentration of the polymer particles is higher and the size of the polymer particles is smaller.
  • US Pat. No. 4,650,841 discloses a method of preventing fouling by reducing catalyst activity using an inactivating agent
  • US Pat. No. 5,733,988 discloses a method of adding alcohol, ether, ammonia, and the like as an antifouling agent. Doing.
  • US Pat. No. 5,270,407 discloses a method for preventing fouling by adding polysiloxane to the catalyst system
  • US Pat. No. 3,956,257 discloses a fouling prevention method using hydrocarbyl aluminum alkoxide.
  • these methods also have a limitation in that the catalytic activity is reduced overall.
  • the present invention aims to solve all the above-mentioned problems.
  • An object of the present invention is to provide a metallocene catalyst system which enables long-term operation of a more stable operation by minimizing fouling and agglomeration while maintaining the inherent activity of the catalyst during polyolefin polymerization through slurry polymerization or gas phase polymerization. .
  • Another object of the present invention is to provide a polyolefin production method using the metallocene catalyst system described above.
  • Another object of the present invention is to provide a polyolefin prepared using the above-described metallocene catalyst system and polyolefin production method.
  • 100 parts by weight of at least one metallocene compound comprising at least one compound selected from the group consisting of sulfates, sulfonates, phosphates and carboxylates and at least one white mineral oil.
  • a composition for operational stabilization comprising at least one compound selected from the group consisting of sulfates, sulfonates, phosphates and carboxylates and at least one white mineral oil.
  • At least one or more white mineral oil provides a metallocene catalyst system comprising at least one or more of the first compound represented by the formula (1) as a composition for the operation stability.
  • M 1 is any one of carbon, sulfur and phosphorus atoms
  • M 2 is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, calcium, strontium, barium and radium
  • a 1 is hydrogen, Oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon number Is an aryloxy group having 6 to 30, at least one substituent of an acetate group, O represents an oxygen atom, R 1 is an alkyl or isoalkyl group having 8 to 20 carbon atoms, alkenyl group having 8 to 20 carbon atoms, carbon number Is an alkynyl group having 8 to 20 and an aryl group having 6 to 30 carbon atoms, and at least one is an integer of 1
  • a metallocene catalyst system wherein the first compound includes a second compound represented by Formula 2 below.
  • M 3 is a sulfur atom
  • M 4 is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium
  • a 2 is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, carbon number Any one or more of alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 30 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, and acetate groups
  • O is an oxygen atom
  • R 2 is an alkyl or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl having 6 to 30 carbon atoms. At least one substituent of the group.
  • a metallocene catalyst system including a compound represented by Chemical Formula 5 is provided.
  • M 5 is a Group 4 transition metal
  • Z 1 and Z 2 are each independently a halogen atom or a methyl group
  • Cp 1 and Cp 2 are the same as or different from each other, and are each independently cyclopentadienyl, indenyl, 4,5 , 6,7-tetrahydro-1-indenyl, and a fluorenyl radical, which may be substituted with one or more hydrocarbon groups having 1 to 20 carbon atoms
  • R 3 and R 4 are the same as each other Or different and each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkoxyalkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aryloxy group of 6 to 10 carbon atoms, or carbon atoms
  • a polyolefin prepared using the above-described polyolefin production method with at least one monomer selected from the group consisting of ethylene and olefinic monomers. do.
  • the present invention is to include a specific operation stability composition in the metallocene catalyst system. By minimizing fouling and agglomeration during polyolefin polymerization, more stable operation can be operated for a long time.
  • the present invention by including a specific operation stability composition in the metallocene catalyst system, the activity inherent to the metallocene catalyst can be maintained without being lowered.
  • the present invention has an effect of improving the ease of mixing and flowability in the catalyst system of the composition for operation stability by including a white mineral oil in the composition for operation stability.
  • Example 1 is a graph comparing the polymerization kinetic when using the catalyst system according to Example 1 and Comparative Example 1 of the present invention.
  • Figure 2 is a graph measuring the temperature change of the inner wall of the reactor during polyolefin polymerization using the catalyst system according to Example 6 of the present invention.
  • the metallocene catalyst system may include at least one metallocene compound and an operation stability composition, and the operation stability composition may be selected from the group consisting of sulfate, sulfonate, phosphate, and carboxylate salts. At least one compound selected and at least one white mineral oil.
  • the white mineral oil has an effect of facilitating mixing of the catalyst composition and the composition for operation stabilization during polymerization by adding at least one compound selected from the group consisting of sulfate, sulfonate, phosphate and carboxylate. This allows the polymer to be formed uniformly in the polymerization reactor.
  • Metallocene catalyst system comprising at least one compound selected from the group consisting of sulphate, sulfonate, phosphate and carboxylate salts as one embodiment of the present invention, the polymer particles in the production of polyolefins by gas phase polymerization or slurry polymerization
  • the intrinsic activity of the catalyst can be stably maintained while minimizing the static electricity generated by friction between the liver or friction between the polymer particles and the inner wall of the reactor. It is assumed that this is because the metallocene catalyst system of the above embodiment forms the particle size and bulk density of the polymer present in the reactor in a range in which generation of static electricity due to friction can be minimized.
  • composition for operating stability may include at least one or more white mineral oil and at least one or more first compounds represented by the following Chemical Formula 1.
  • M 1 is any of carbon, sulfur, phosphorus atoms
  • M 2 is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, calcium, strontium, barium and radium;
  • a 1 is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, and 1 to 10 carbon atoms.
  • O means oxygen atom
  • R 1 is a substituent of any one of an alkyl group or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms;
  • n is an integer of 1 or 2.
  • the first compound may include a second compound represented by Formula 2 below.
  • M 3 is a sulfur atom
  • M 4 is any one selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium;
  • a 2 is hydrogen, oxygen, alkyl or isoalkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, and 1 to 10 carbon atoms.
  • O means oxygen atom
  • R 2 is a substituent of any one of an alkyl group or isoalkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an alkynyl group having 8 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms.
  • the second compound is preferably at least one selected from sodium dodecylsuflate (SDS) represented by the following Chemical Formula 3 and sodium lauryl sulfoacetate (SLSA) represented by the following Chemical Formula 4 It may include.
  • SDS sodium dodecylsuflate
  • SLSA sodium lauryl sulfoacetate
  • the effect of improving the stabilization of the operation may be similar after the improvement to a certain limit, but the activity of the catalyst may be reduced by reacting the excess stabilizer composition with the catalyst.
  • composition for operation stability comprising at least one or more white mineral oils described above and at least one compound selected from the group consisting of sulfates, sulfonates, phosphates and carboxylates is based on 100 parts by weight of the metallocene catalyst compound. To 300 parts by weight, preferably 30 to 200 parts by weight.
  • the metallocene catalyst system according to the present invention may include a conventional metallocene compound, the configuration is not particularly limited.
  • the metallocene compound may be a compound represented by Formula 5 below:
  • M 5 is a Group 4 transition metal
  • Z 1 and Z 2 are each independently a halogen atom or a methyl group
  • Cp 1 and Cp 2 are the same as or different from each other, and each independently one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals Which may be substituted with one or more hydrocarbon groups of 1 to 20 carbon atoms;
  • R 3 and R 4 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms
  • R 5 cross-links (Cp 1 R 3 ) and (Cp 2 R 4 ) by a covalent bond, a divalent hydrocarbon containing an element selected from the group consisting of methyl groups or silicon, germanium, phosphorus, nitrogen, boron and aluminum Group;
  • n 0 or 1
  • M 5 may be an element such as Ti, Zr, Hf, etc.
  • Group 4 transition metal, R 5 is preferably in the methyl group, silicon, germanium, phosphorus, nitrogen, boron and aluminum It may include any one.
  • the metallocene compound is BisIndenylZrCl 2 , BisIndenylHfCl 2 , Bis (1-butyl-3-methylcyclopentadienyl) ZrCl 2 , Bis (cyclopentadienyl) ZrCl 2 , rac-Ethylene-1,2-bis (1-indenyl ) ZrCl 2 , rac-Dimethylsilylene-bis (1-indenyl) ZrCl 2 , (Cyclopentadienyl) IndenylZrCl 2 , [Dimethylsilyl ( ⁇ 5-tetramethylCyclopentadienyl) (t-butylamido)] TiCl 2, and the like.
  • the metallocene catalyst system according to the present invention may further include a cocatalyst compound.
  • the promoter compound may be a conventional compound capable of activating the metallocene compound, preferably at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 9.
  • Al is aluminum
  • R 6 , R 7 and R 8 are each independently hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms;
  • p is an integer of 2 or more
  • M 6 is aluminum or boron
  • Each R 9 is independently hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms, or alkoxy having 1 to 20 carbon atoms;
  • L 1 and L 2 are each independently neutral or cationic Lewis bases
  • [L 1 -H] + or [L 2 ] + is a Bronsted acid
  • M 7 and M 8 are each independently a Group 13 element of the Periodic Table of the Elements;
  • R 10 and R 11 each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, unsubstituted or substituted with halogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy or phenoxy radical having 1 to 20 carbon atoms It is a substituted C1-C20 alkyl group.
  • the compound represented by the formula (6) is aluminoxane, and is not particularly limited as long as it is an ordinary alkylaluminoxane.
  • methyl aluminoxane ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like can be used, and specifically, methyl aluminoxane can be used.
  • the alkylaluminoxane may be prepared by a conventional method such as adding an appropriate amount of water to trialkylaluminum, or reacting a trialkylaluminum with a hydrocarbon compound or an inorganic hydrate salt containing water, and is generally linear and cyclic. Aluminoxanes are obtained in mixed form.
  • a conventional alkyl metal compound can be used as the compound represented by the formula (7).
  • Examples of the compound represented by the formula (8) or (9) include methyldioctateylammonium tetrakis (pentafluorophenyl) borate ([HNMe (C18H37) 2] + [B (C6F5) 4]-), trimethylammonium tetrakis ( Phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetrakis (phenyl) borate, tributylammonium tetrakis (phenyl) borate, trimethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, triethylammonium tetrakis (o, p-dimethylphenyl) bo
  • methyldioctateylammonium tetrakis (pentafluorophenyl) borate [HNMe (C18H37) 2] + [B (C6F5) 4]-
  • N, N-dimethylanilinium tetrakis (pentafluorophenyl ) Borate triphenylcarbonium tetrakis (pentafluorophenyl) borate, and the like.
  • the promoter compound is 1: 1 to 1: 10,000, or 1: 1 to 1: 1,000, based on the molar ratio of the metal contained in the promoter compound to 1 mol of the transition metal contained in the metallocene compound. Or 1: 1 to 1: 100.
  • the metallocene compound, the composition for operation stability, and the cocatalyst compound may be a supported catalyst supported on a carrier.
  • the catalyst may be supported on a carrier to maintain a good dispersion and stability in order to improve catalyst activity and maintain stability.
  • the carrier is a solid that disperses and retains the catalytically functional material stably, and is usually a porous or large-area material for highly dispersed and supported so as to increase the exposed surface area of the catalytically functional material.
  • the carrier must be mechanically, thermally and chemically stable.
  • the carrier is not limited in kind, and may include all carriers that can be used as a carrier, and may be, for example, silicon compounds including silica, alumina, titanium compounds, bauxite, zeolite, zinc oxide, starch, synthetic polymers, and the like. Preferably, it may be silica, but is not limited thereto.
  • the carrier may have an average particle size of 10 to 250 microns, preferably an average particle size of 10 to 150 microns, and more preferably 20 to 100 microns.
  • the micropore volume of the carrier may be 0.1 to 10 cc / g, preferably 0.5 to 5 cc / g, more preferably 1.0 to 3.0 cc / g.
  • the specific surface area of the carrier may be 1 to 1000 m 2 / g, preferably 100 to 800 m 2 / g, and more preferably 200 to 600 m 2 / g.
  • the silica when the carrier is silica, the silica may be a drying temperature of 200 to 900 °C. Preferably from 300 to 800 ° C, more preferably from 400 to 700 ° C. If the temperature is less than 200 ° C., there is too much water, and the surface of the surface reacts with the promoter, and if it exceeds 900 ° C., the carrier collapses.
  • the concentration of the hydroxy group in the dried silica may be 0.1 to 5 mmol / g, preferably 0.7 to 4 mmol / g, more preferably 1.0 to 2 mmol / g. If the amount is less than 0.5 mmol / g, the supported amount of the promoter is low, and if the amount exceeds 5 mmol / g, there are problems in that the catalyst component is inactivated due to many side reactions.
  • the supported catalyst according to the above embodiment is suspended by stirring silica gel and slowly adding a cocatalyst compound (methyl aluminoxane, etc.), and then adding an operation stability composition and a metallocene compound thereto, and stirring It can be prepared through a washing, drying process.
  • a cocatalyst compound methyl aluminoxane, etc.
  • the metallocene catalyst can be prepared by supporting the metallocene compound and the promoter compound according to the present invention by supporting them on a carrier.
  • the solvent for the reaction in the preparation of the metallocene catalyst is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, diethyl ether or tetrahydrofuran (THF) It may be an organic solvent such as ether solvent, acetone, ethyl acetate, and the like, preferably toluene, hexane, but is not limited thereto.
  • an organic solvent such as ether solvent, acetone, ethyl acetate, and the like, preferably toluene, hexane, but is not limited thereto.
  • the metallocene compound can be activated by mixing (contacting) the promoter compound.
  • the mixing can be carried out in the presence of the hydrocarbon solvent, or without the solvent, usually under an inert atmosphere of nitrogen or argon.
  • the temperature may be 0 to 100 ° C, preferably 10 to 30 ° C, and a time may be 5 minutes to 24 hours, and preferably 30 minutes to 3 minutes. It can be time.
  • the metallocene compound may be used as it is, or the catalyst composition in a solution state uniformly dissolved in the hydrocarbon solvent or the like, or in a solid powder state in which the solvent is removed, but is not limited thereto.
  • composition for operating stability of the present invention is prepared by stirring the compound represented by the formula (1) and the white mineral oil at a temperature of 500 to 3000 rpm for 30 minutes to 24 hours, preferably 2 to 4 hours at a temperature of room temperature to 90 °C can do.
  • the step of polymerizing at least one monomer selected from the group consisting of ethylene and olefinic monomers using gas phase polymerization or slurry polymerization A method for producing a polyolefin is provided.
  • the polymerization reactor may use any one or more of a batch reactor, a continuous reactor and a gas phase polymerization reactor.
  • a solvent or olefin itself can be used as the medium.
  • the solvent includes propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, chloro Benzene and the like can be exemplified, and these solvents may be mixed and used in a predetermined ratio, but are not limited thereto.
  • examples of the olefin monomers include ethylene, ⁇ -olefins, cyclic olefins, and the like, and preferably, ⁇ -olefins having 2 to 20 carbon atoms, diolefins having 1 to 20 carbon atoms, and 3 carbon atoms. At least one compound selected from the group consisting of cycloolefins having from 20 to 20 and cyclodiolefins having from 3 to 20 carbon atoms. Even more preferably, it may be, but is not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, mixtures thereof.
  • the ⁇ -olefins may have 3 to 12 carbon atoms, for example, include aliphatic olefins having 3 to 8 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, and 3-methyl-1-butene , 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 4,4-dimethyl-1-pentene, 4, 4-diethyl-1-hexene, 3,4-dimethyl-1-hexene and the like can be exemplified, but is not limited thereto.
  • the ⁇ -olefins may be polymerized singly or two or more olefins may be alternating, random, or block copolymerized.
  • Copolymerization of the ⁇ -olefins is copolymerization of ethylene and an ⁇ -olefin having 3 to 12 carbon atoms, for example, 3 to 8 (specifically, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, and ethylene 4-methyl-1-pentene, such as ethylene and 1-octene) and copolymerization of propylene with an ⁇ -olefin having 4 to 12 carbon atoms, for example 4 to 8 carbon atoms (specifically, propylene and 1-butene, propylene and 4- Methyl-1-pentene, propylene and 4-methyl-1-butene, propylene and 1-hexene, propylene and 1-octene, and the like.
  • the amount of other ⁇ -olefins may be up to 99 mole percent of the total monomers, typically for ethylene copolymers up to 80 mole percent.
  • 1,3-butadiene, 1,4-pentadiene, and 2-methyl-1,3-butadiene (2-methyl- Diolefin having 1 to 20 carbon atoms including 1,3-butadiene); 3 carbon atoms, including cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, and methyl-2-norbonene Cycloolefin or cyclodiolefin of 20 to 20;
  • Substituted styrene in which an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a halogen group, an amine group, a silyl group, a haloalkyl group, or the like is bonded to a styrene ring or a phenyl ring of styrene; Or mixtures thereof.
  • the temperature and pressure during the polymerization is not particularly limited because it may vary depending on the reaction materials, reaction conditions, etc.
  • the polymerization temperature may be 0 to 120 °C in the case of slurry or gas phase polymerization, preferably 60 to 100 °C Can be.
  • the polymerization pressure may be 1 to 150 bar, preferably 5 to 50 bar, more preferably 10 to 20 bar.
  • the pressure may be by injection of an olefin monomer gas (eg ethylene gas).
  • the catalytic activity is superior to other conditions, and fouling and agglomeration are reduced.
  • the composition for stabilizing the operation according to the present invention in a specific content ratio.
  • the polymerization can also be carried out in two or more steps with different reaction conditions, and the molecular weight of the final polymer can be controlled by varying the polymerization temperature or by injecting hydrogen into the reactor.
  • MAO and metallocene catalyst compounds which are cocatalysts used in the catalyst, lose their activity when they react with moisture and oxygen in the air. Therefore, all experiments were conducted under nitrogen condition using Glove Box and Schlenk Technique.
  • the 10 L supported catalytic reactor is washed to remove foreign substances and the reactor is vacuumed to remove internal air using a vacuum for at least 10 minutes.
  • Mineral oil and sodium dodecyl sulfate which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions.
  • 7.5 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at a speed of rpm.
  • Mineral oil and sodium dodecyl sulfate which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 10 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) to 1000 Stir at room temperature for 3 hours at rpm.
  • Mineral oil and sodium lauryl sulfoacetate which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions.
  • 7.5 g of sodium lauryl sulfoacetate (CAS.No. 1847-58-1; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at 1000 rpm.
  • Mineral oil and sodium lauryl sulfoacetate components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions.
  • 10 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) to 1000 Stir at 90 ° C. for 3 hours at a speed of rpm.
  • Mineral oil and sodium lauryl sulfoacetate components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 0.25 g of sodium lauryl sulfoacetate (CAS.No. 1847-58-1; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at 1000 rpm.
  • Mineral oil and sodium dodecyl sulfate which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions. 0.25 g of sodium dodecyl sulfate (CAS.No.151-21-3; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) Stir at 90 ° C. for 3 hours at a speed of rpm.
  • Mineral oil and sodium lauryl sulfoacetate which are components of the composition for operation stability, are used in a state where water and the like are completely removed under vacuum and nitrogen conditions.
  • 35 g of sodium lauryl sulfoacetate (CAS.No. 1847-58-1; Miwon Co.) was added to 30 g of white mineral oil (CAS.No.8042-47-5; S-oil total finavestan A360B) stir at 90 ° C. for 3 hours at 1000 rpm.
  • the resin shape obtained through the polymerization was compared through the Fouling index used in the present specification, and the results are shown in Table 2 together with the catalytic activity.
  • the fouling index categorizes fouling and agglomeration within the polymerization reactor walls and agitators into the resulting polymer form.
  • Fouling index 0 no fouling and agglomeration
  • Fouling index 1 Agglomeration of the polymer less than 1 cm (polymer diameter)
  • Fouling index 2 Agglomeration of the polymer 1-2 cm
  • Fouling index 3 Agglomeration of the polymer 2 ⁇ 4 cm
  • Fouling index 4 Polymer of film form 4 ⁇ 6 cm
  • Fouling index 5 6 ⁇ 8 cm film polymer
  • Fouling index 6 Reactor wall sheet formation
  • Example 1 The polymerization kinetic of Example 1 was measured and the result is shown in FIG.
  • a polyolefin (172 g) was prepared in the same manner as in Example 1 except for injecting 50 mg of the composition for operation stability of Preparation Example 2, and the operating conditions of the polymerization reaction are shown in Table 1 below.
  • the polymer coating was not present in the wall and the stirrer.
  • a polyolefin (206 g) was prepared in the same manner as in Example 1 except that 25 mg of the composition for operating stability of Preparation Example 3 was prepared, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was not present in the wall and the stirrer.
  • a polyolefin (168 g) was prepared in the same manner as in Example 1 except that 16 mg of the composition for operating stability in Preparation Example 4 was injected, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was not present in the wall and the stirrer.
  • a polyolefin (173 g) was prepared in the same manner as in Example 1 except for injecting 15 mg of the composition for operation stability of Preparation Example 5, and the operating conditions of the polymerization reaction are shown in Table 1 below.
  • Polyolefin (170 g) was prepared in the same manner as in Example 1, except that the composition for operation stability was not included, and the operating conditions of the polymerization reaction are shown in Table 1 below.
  • the polymer coating was present on the wall and the stirrer.
  • a polyolefin (154 g) was prepared in the same manner as in Example 1 except for injecting the composition for operating stability of Preparation Example 6, and the operating conditions of the polymerization reaction are shown in Table 1 below.
  • the polymer coating was present on the wall and the stirrer.
  • a polyolefin (150 g) was prepared in the same manner as in Example 4 except for injecting the composition for operating stability of Preparation Example 7, and the operating conditions of the polymerization reaction are shown in Table 1 below.
  • the polymer coating was present on the wall and the stirrer.
  • a polyolefin (62 g) was prepared in the same manner as in Example 4 except for injecting the composition for operating stability of Preparation Example 8, and the operating conditions of the polymerization reaction are shown in Table 1 below.
  • the polymer coating was present on the wall and the stirrer.
  • a polyolefin (74 g) was prepared in the same manner as in Example 1 except that 100 mg of the composition for operation stability of Preparation Example 2 was prepared, and the operating conditions of the polymerization reaction are shown in Table 1 below. The polymer coating was not present in the wall and the stirrer.
  • a polyolefin was prepared in the same manner as in Example 6 except that the composition for operation stability was not included.
  • Temperature change of the inner wall surface was measured through a static probe in the polyethylene manufacturing process, the results are shown in FIG. As can be seen from the change in the temperature line in Figure 3, after about 18 hours after the catalyst injection, the temperature of the reactor wall rapidly rises (hot spot) occurs to produce a sheet and chunk, continuous operation was not possible. At this time, the static average value was measured as -1.899 kV.
  • Example 6 Comparative Example 6 C2 PP (K / G) 14.2 14.08 Static (kV) -1.21 -1.899 Temp. (°C) 82 85 UBD (g / cc) 0.288 0.239 H2 / C2 (%) 0.13 0.13 C6 / C2 (%) 0.96 0.821 Active (kgPE / kgCat.) 6000 6000 MI (g / min) 1.35 0.925 Bulk Density (g / cm 3 ) 0.479 0.495
  • Example 1 to 6 all of the fouling index (fouling index) is an index for indicating the fouling phenomenon was not observed, especially in the sixth embodiment of the gas phase polymerization, the reactor wall temperature is kept stable Although it can be confirmed that the operation can be performed even for a long time of 50 hours or more, in the case of Comparative Example 1, which does not include the composition for operating stability, the fouling index was found to be 3, and the fouling phenomenon was observed. In Comparative Example 6, the wall temperature of the reactor rapidly increased from about 18 hours after the catalyst injection (hot spot) occurred. It can be confirmed that continuous operation is impossible due to sheet and chunk.
  • Example 6 shows that the reactor wall temperature is stably as shown in the change of the temperature lines of FIG. It can be confirmed that stable operation for more than 50 hours is possible.
  • the composition for operating stability is preferably 30 to 300, or particularly preferably 30 to 200% by weight. However, depending on the composition of the composition, the appropriate amount of the composition for operation stability is fluid.
  • Preparation Example 2 for the operation stability of the catalyst As the content of the composition for operation stability increases, it is operationally stable without significant change in fouling and agglomeration phenomenon inside the stirrer, but the polymerization activity decreases. This can be confirmed by Comparative Example 5.
  • Comparative Example 5 was included in the stabilizer composition 330% by weight, it was confirmed that the catalyst activity sharply dropped.
  • the metallocene supported catalyst is advantageously present in an amount of 1: 2 or less based on the weight of the composition for operating stability.
  • the composition for operation stability includes a white mineral oil and a composition of Formula 1, wherein the composition of Formula 1 may include 1 to 50% by weight based on the total weight of the operation stability composition. If the composition of Formula 1 is in an amount ratio of 1 to 50% by weight, it may have an optimum operation stability by appropriately adjusting the content ratio of the composition and the supported catalyst for the operation stability, but if it is out of this the content ratio of the composition and the supported catalyst for operation stability Even if control is controlled, operations may become unstable due to problems such as flowability and phase separation.
  • the amount of the composition of the formula (1) required to exhibit the operation stability during polymerization should be added, and accordingly 99% or more of mineral oil
  • the method of using the composition for operational stability of the containing form is wasteful.
  • a phase separation phenomenon with the white mineral oil occurs, which may cause the input instability in the reactor and adversely affect the polymerization operation stability, which can be confirmed through Comparative Examples 2 and 3.
  • composition for operation stability is preferably produced at a temperature range lower than the melting point of the composition represented by the formula (1), and particularly preferably, can be prepared at a temperature range from room temperature to 90 °C.
  • the polyolefin polymerization process according to the invention can be carried out on an industrial scale, no coatings occur and no aggregates are formed, the productivity of the catalysts used is increased and can have good morphology.

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Abstract

La présente invention concerne un système catalyseur métallocène comprenant une composition fonctionnellement stable, et un procédé de production de polyoléfine au moyen du système catalyseur métallocène. Plus particulièrement, en utilisant le système catalyseur métallocène comprenant : de 90 à 99,9 % en poids de composé métallocène d'un ou plusieurs types ; et de 0,1 à 10 % en poids d'une composition fonctionnellement stable comprenant un ou plusieurs types de composés choisis dans le groupe constitué par un sulfate, un sulfonate, un phosphate et un carboxylate, et un ou plusieurs types d'huile minérale blanche, l'activité unique du catalyseur est maintenue et les phénomènes d'encrassement et d'agglomération sont réduits au minimum pendant la polymérisation d'oléfines pour permettre au procédé d'être mis en œuvre de manière stable, et ainsi au moyen de la présente invention, un procédé de production de polyoléfine peut être fourni, et une polyoléfine produite peut être fournie.
PCT/KR2017/014020 2016-12-01 2017-12-01 Système catalyseur métallocène comprenant une composition fonctionnellement stable, et procédé de production de polyoléfine au moyen d'un système catalyseur métallocène Ceased WO2018101794A2 (fr)

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